CA2068116A1 - Stabilized hot melt adhesive systems - Google Patents
Stabilized hot melt adhesive systemsInfo
- Publication number
- CA2068116A1 CA2068116A1 CA002068116A CA2068116A CA2068116A1 CA 2068116 A1 CA2068116 A1 CA 2068116A1 CA 002068116 A CA002068116 A CA 002068116A CA 2068116 A CA2068116 A CA 2068116A CA 2068116 A1 CA2068116 A1 CA 2068116A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- formula
- hydrogen
- group
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000004831 Hot glue Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 48
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 11
- 239000002516 radical scavenger Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims abstract description 4
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- -1 alkali metal salts Chemical class 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 239000002530 phenolic antioxidant Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 11
- 235000019198 oils Nutrition 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 229910052717 sulfur Chemical group 0.000 claims description 5
- 239000011593 sulfur Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000012169 petroleum derived wax Substances 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 2
- 125000002861 (C1-C4) alkanoyl group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- MALIONKMKPITBV-UHFFFAOYSA-N 2-(3-chloro-4-hydroxyphenyl)-n-[2-(4-sulfamoylphenyl)ethyl]acetamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1CCNC(=O)CC1=CC=C(O)C(Cl)=C1 MALIONKMKPITBV-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000002845 discoloration Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 8
- 229920006270 hydrocarbon resin Polymers 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003209 petroleum derivative Substances 0.000 description 6
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 1
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- IOHCSOXUCWUZQJ-UHFFFAOYSA-J 2,2'-spirobi[1,3,2-benzodioxastannole] Chemical compound O1c2ccccc2O[Sn]11Oc2ccccc2O1 IOHCSOXUCWUZQJ-UHFFFAOYSA-J 0.000 description 1
- BVNPSIYFJSSEER-UHFFFAOYSA-H 2-[2-(1,3,2-benzodioxastibol-2-yloxy)phenoxy]-1,3,2-benzodioxastibole Chemical compound O([Sb]1Oc2ccccc2O1)c1ccccc1O[Sb]1Oc2ccccc2O1 BVNPSIYFJSSEER-UHFFFAOYSA-H 0.000 description 1
- VXBVLYQDVVHAHZ-UHFFFAOYSA-N 3-methylidenepenta-1,4-diene Chemical compound C=CC(=C)C=C VXBVLYQDVVHAHZ-UHFFFAOYSA-N 0.000 description 1
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- SMISHRXKWQZCCQ-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-3-yl) decanedioate Chemical compound CC1(C)N(C)C(C)(C)CCC1OC(=O)CCCCCCCCC(=O)OC1C(C)(C)N(C)C(C)(C)CC1 SMISHRXKWQZCCQ-UHFFFAOYSA-N 0.000 description 1
- YWDBZVIHZORXHG-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-1-yl) decanedioate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)CCCCCCCCC(=O)ON1C(C)(C)CCCC1(C)C YWDBZVIHZORXHG-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QITVMFSGIKQAFH-UHFFFAOYSA-N n'-(2,2,6,6-tetramethylpiperidin-1-yl)hexane-1,6-diamine Chemical compound CC1(C)CCCC(C)(C)N1NCCCCCCN QITVMFSGIKQAFH-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
STABILIZED HOT MELT ADHESIVE SYSTEMS
Abstract of the Disclosure Hot melt adhesive compositions stabilized against thermal degradation, discoloration, skin formation and substantial viscosity changes, said adhesives being based on ethylene-vinyl acetate copolymer and a hydrocarbon tackifying resin and containing a stabilizer system of a hindered phenol antioxidant, a phosphite costabilizer and an acid scavenger.
Abstract of the Disclosure Hot melt adhesive compositions stabilized against thermal degradation, discoloration, skin formation and substantial viscosity changes, said adhesives being based on ethylene-vinyl acetate copolymer and a hydrocarbon tackifying resin and containing a stabilizer system of a hindered phenol antioxidant, a phosphite costabilizer and an acid scavenger.
Description
206811~
STABILlZED HOT MELT ADHESIVE SYSTEMS
Hot melt adhesives, including those based on ethylene vinyl acetate copolymer, are especially susceptible to oxidation due to high temperature (180C) compounding, storage, handling and application. As the perfoTmance requirements for such adhesives increased, the use of antioxidants evolved to prevent discoloration, undesirable viscosity changes and skin formation on the surface of the adhesive. Hindered phenols were the primary antioxidant of choice for stabilization of the adhesive systems.
A further approach to achieving stabilization beyond that provided by the hindered phenols involved the use of secondary antioxidants such as thiosynergists or phosphite stabilizers including triarylphosphites. The combination of primary and secondary antioxidants provided stabilization performance beyond that which could be expected based on the sum of the performance of the individual components.
A complication was, however, encountered by the frequent use of white or light colored hydrocarbon tackifying resins in adhesive formulations where good color stability is ~equired.
Thus, negative interactions were experienced with such hydrocarbon tacldfiers as evidenced by way of gray-black discoloration upon heating. Since it was hypothesized that the interactions involved the phosphite costabilizer, the applicability of the latter has been substantially reduced. Accordingly, solutions to this problem are required which eliminate the discoloration effect while still preserving the effective properties provided by the presence of the tackifler and the phosphite costabilizer.
Background material on these issues are provided by the following: US-A-4,360,617 which discloses blends of phenols and symmetrical triarylphosphites for stabilizing a broad range of organic polymers including elastomers and ethylene-vinyl acetate copolymers;
US-A-3,658,743 which discloses synergistic combinations of phenols, an organic sulfide or thioester and an epoxide or phosphite ester for the stabilization of hydrocarbon elastomers;
US-A-4,835,200 which discloses stabilizer systems of a thio compound, a phenolic 2068~16 antioxidant, a tris(nonylated phenyl)phosphite and an aliphatic compatible epoxy compound for use in various tackified block copolymer resin systems; and US-A4,857,572 which discloses (alkylthioaUcyl) phenols with optional addidon of phosphites for use in stabilizing various elastomers.
It has now been surprisingly discovered that a unique combination of primary and secondary antioxidants and of an acid scavenger substandaUy eliminates the aforemendoned difficuldes encountered in the stabilizadon of ethylene-vinyl acetate hot melt adhesives containing hydrocarbon tackifying resins. Thus, the blend of hindered phenol, phosphite and acid scavenger provides color stability while m~nimizing viscosity changes, heat degradadon and skin forrnadon. By facilitadng the use of phosphite costabilizers, the combinadon provides stabilization properties which additionaUy exceed the performance of the individual state of the art andoxidants.
The invention pertains to a stabilized hot melt adhesive composition comprising (a) ethylene-vinyl acetate copolymer;
(b) a hydrocarbon tackifying resin; and (c) a stabilizer composition comprising (1) a phenolic antioxidant;
STABILlZED HOT MELT ADHESIVE SYSTEMS
Hot melt adhesives, including those based on ethylene vinyl acetate copolymer, are especially susceptible to oxidation due to high temperature (180C) compounding, storage, handling and application. As the perfoTmance requirements for such adhesives increased, the use of antioxidants evolved to prevent discoloration, undesirable viscosity changes and skin formation on the surface of the adhesive. Hindered phenols were the primary antioxidant of choice for stabilization of the adhesive systems.
A further approach to achieving stabilization beyond that provided by the hindered phenols involved the use of secondary antioxidants such as thiosynergists or phosphite stabilizers including triarylphosphites. The combination of primary and secondary antioxidants provided stabilization performance beyond that which could be expected based on the sum of the performance of the individual components.
A complication was, however, encountered by the frequent use of white or light colored hydrocarbon tackifying resins in adhesive formulations where good color stability is ~equired.
Thus, negative interactions were experienced with such hydrocarbon tacldfiers as evidenced by way of gray-black discoloration upon heating. Since it was hypothesized that the interactions involved the phosphite costabilizer, the applicability of the latter has been substantially reduced. Accordingly, solutions to this problem are required which eliminate the discoloration effect while still preserving the effective properties provided by the presence of the tackifler and the phosphite costabilizer.
Background material on these issues are provided by the following: US-A-4,360,617 which discloses blends of phenols and symmetrical triarylphosphites for stabilizing a broad range of organic polymers including elastomers and ethylene-vinyl acetate copolymers;
US-A-3,658,743 which discloses synergistic combinations of phenols, an organic sulfide or thioester and an epoxide or phosphite ester for the stabilization of hydrocarbon elastomers;
US-A-4,835,200 which discloses stabilizer systems of a thio compound, a phenolic 2068~16 antioxidant, a tris(nonylated phenyl)phosphite and an aliphatic compatible epoxy compound for use in various tackified block copolymer resin systems; and US-A4,857,572 which discloses (alkylthioaUcyl) phenols with optional addidon of phosphites for use in stabilizing various elastomers.
It has now been surprisingly discovered that a unique combination of primary and secondary antioxidants and of an acid scavenger substandaUy eliminates the aforemendoned difficuldes encountered in the stabilizadon of ethylene-vinyl acetate hot melt adhesives containing hydrocarbon tackifying resins. Thus, the blend of hindered phenol, phosphite and acid scavenger provides color stability while m~nimizing viscosity changes, heat degradadon and skin forrnadon. By facilitadng the use of phosphite costabilizers, the combinadon provides stabilization properties which additionaUy exceed the performance of the individual state of the art andoxidants.
The invention pertains to a stabilized hot melt adhesive composition comprising (a) ethylene-vinyl acetate copolymer;
(b) a hydrocarbon tackifying resin; and (c) a stabilizer composition comprising (1) a phenolic antioxidant;
(2) a phosphite c~stabilizer, and (3) an acid scavenger selected from the group consisting of epoxidized oils, alkali metal salts of higher fatty acids, alkaline earth metal salts of higher fatty acids and amines.
The primary components of the hot melt adhesive system are ethylene-vinyl acetate copolymer, a hydrocarbon tackifying resin and, opdonally, petroleum derived waxes and various plasticizing oils.
The applicable tackifying resins may be described as hydrogenated and non-hydrogenated aliphatic petroleum hydrocarbon resins (preferably hydrogenated varieties) resulting from the polymerization of monomers consisting primarily of mono- and diolefins, hydrogenated and non-hydrogenated aromatic petroleum hydrocarbon resins and hydrogenated and non-hydrogenated alicyclic petroleum hydrocarbon resins. Additionally, hydrogenated and non-hydrogenated polyteIpene hydrocarbon resins may be used as the tackifying resin.
Mixtures of the above are also applicable. Such tackifying resins for example are present in concentrations ranging from 10 to 90%, by weight, and preferably 2S to 50%, by weight. The particular resin is selected on the basis of compatibility with the adhesive system, with 20~811~
colorless or white tacldfiers being paTticularly preferred. (~)ARKON P-90 from Arakawa Chemical, (~)ESCOREZ 5300 from Exxon Chemical and ~\REGALREZ 1094 from Hercules,for example, are typical commercial tacldfying resins.
Preferred composidons are those, wherein said hydrocarbon tackifying resin is selected from the group consisting of aliphatic petroleum hydrocarbon resins and hydrogenated derivatives thereof, aromadc petroleum hydrocarbon resins and hydrogenated deIivatives thereof and alicyclic petroleum hydrocarbon resins and hydrogenated derivatives thereof, polyterpene hydrocarbon resins and hydrogenated derivatdves thereof, and mixtures thereof. Pardcularly preferred are those, wherein said hydrocarbon tackifying resin is hydrogenated.
The petroleum derived waxes are optionally present in concentrations ranging from 0 to 50%, by weight, and serve to impart greater fluidity to the molten mateAal, flexibility to the set adhesive and wefflng characteristics. Paraffin and microcrystalline waxes with melting points of 55-110C as well as polyethylene or Fischer-Tropsch waxes are illustrative of this component.
The composition described above may additionally contain (d) up to 50% by weight of a petroleum derived wax, based on components (a) and (b). In these compositions components (a), (b) and (d) are preferably present in a weight ratio of 1:1:1.
These plasticizing or extending oils are also present in order to provide wetting action and viscosity control. Concentrations from 1 to 50%, by weight, are applicable. Typical oils include ole~m oligomers, vegetable and animal oils and naphthenic oils.
In the compositions of the present invention components (a) and (b) are present in a weight ratio of 10:90 to 90:10, especially 25:75 to 75:25.
The combination of stabilizers which substantially eliminates heat degradation, color formation, undesirable viscosity changes and sldn formation comprise (1~ a hindered phenolic antioxidant;
(2) a phosphite co-stabilizer; and (3) an acid scavenger.
206811 ~
Hindered phenols are well known to those skilled in the art.
The composition of the present invention comprises hindered phenolic antioxidants corresponding to the formulae RlX~(CIlH2a)~Q (1) wherein Rl is a group of the formula Ia, H~}(CbH2b)-- I-- (Ia) X is oxygen or sulfur, a is an integer from 6 to 30, preferably 6 to 18, b is an integer from 0 to 6, R2 and R3 are independently Cl-Cl8aL~cyl, Cs-Cl2cycloaL~yl, phenyl or CrC9aralkyl, and R2 is also hydrogen, Q is hydrogen or -A-(C~H2y)~R4~ A is oxygen, sulfur or--Nl--, y iS an integer from 2 to 20, I3 is Cl-C4aL~cyl or Cl-C4alkanoyl, and R4 is hydrogen, hydroxy, Cl-C4alkanoyloxy or a group of the formula Ib, H~(CbH2b)--C---- (Ib);
u~(CbH2b)--C--o~Ql wherein R2, R3 and b are as defined above, r is 1, d is an integer from 2 to 6, and Ql is a divalent aliphatic hydrocarbon of 1 to 18 carbon atoms, a divalent aromatic or aromatic aliphatic hydrocarbon of 6 to 20 carbon atoms or a group of the formula Ila when r is also 0 206~116 (H2C)f N N--(CH2)~
O~N~o (IIa) (Cl H2~f wherein f is an integer from 1 to 4;
L ~ (CbH2b)--C--1 ~ Q2 wherein R2, R3 and b are as defined above, and Q2 iS Cl-C18alkylene;
RlX-[(CzH2~)~Ye~R5 aV) wherein Rl and X are as defined above, z is an integer ~om 2 to 6, e is an integer from 3 to 40, preferably 3 to 10, Y is oxygen or sul~r, and Rs is hydrogen, Cl-C4aLlcyl or a group of the formula Ia;
2 ~
(H3C)3C C(CH3)3 HO~CHH~OH
CH3 ¦ H3C
CHCH3 (V);
H3C~p~
~\C(CH3)3 OH
OH OH
R6~ ~R6 R~ Al~R7 (VI) wherein R6 and R7 are independendy Cl-Cl8alkyl, Cs-C~2cycloaL~cyl, phenyl or C7-C9araL~cyl, and R6 is also hydrogen, and Al is a group ~C(Rg)Rg wherein R8 and Rg are independently hydrogen or Cl-C6aLIcyl;
OH
R3~ l H3C--C--(CpH2p)--C--O- -3 (VII) OH
wherein R3 iS as defined above, p is 1 or 2 and Q3 iS C2-CIOalkylene; and OH
Rl~CHz--S--Rll CH2~ S--Rl 1 wherein Rlo is Cl-ClOallyl or Cs-CI2cycloaL~cyl, Rll independently is Cl-C18alkyl, phenyl or benzyl and R12 iS hydrogen or methyl.
ALkyl is straight chain or branched as for example methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, decyl, undecyl, dodecyl or octadecyl.
Cl-CI8alkyloxy is for example methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy or octadecyloxy.
Cl-C4alkanoyl is for example acetyl, propionyl or butyryl.
Cl-C4aL~canoyloxy is for example acetyloxy, propionyloxy or butyryloxy.
C5-Cl2cycloaL~cyl is for example cyclopentyl, cyclohexyl or cyclooctyl. Cyclohexyl is preferred.
CTCgarallyl is in particular C7-CgphenylaL~cyl~ for example benzyl, a-methylbenzyl, a,a-dimethylbenzyl orphenylethyl. Benzyl is preferred.
Cl-CI8alkylene is for exa nple methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene.
For compounds of forrnula II when r is 1, Ql as a divalent hydrocarbon is e.g. straight-chain or branched C2-Cl8aL~tylene, preferably C2-CIOallcylene, or C2-C6aL~ylidene such as, for example, ethylene, ethylidene, tIimethylene, tetramethylene, pentamethylene, 2,2~imethylpropane-1,3-diyl, hexamethylene, heptamethylene, octarnethylene, 206~
decamethylene, 2,2-pentamethylene-propane-1,3-diyl, and cyclohexylene or Ql as a divalent aromatic or aliphatic aromatic hydrocarbon of 6 to 20 carbon atoms is e.g. unsubstituted or substituted C6-ClOarylene such as, for example, phenylene, phenylene substituted by one or more, for example 1 to 3 Cl-C4aL~cyl, naphthylene or ~ C~
Ql as a trivalent, tetravalent or pentavalent hydrocarbon is, for exarnple, a group of the following formulae b ~ ~ ~,~
alkanetriyl of 3 to 6 carbon atoms, such as e.g. glyceryl or trimethylylpropane or alkanetetrayl of 4 to 6 carbon atoms such as e.g. pentaerythrityl.
Formula Ia represents preferably one of the following groups:
(H3C)3C (H3C)3C
H~ CH2CH2--C-- ~ H~ CH2CHz--C--(H3c)3c H3C
Formula Ib is in particular one of the groups (H3C)3C (H3C)3C
H~ CH2CHz--~C--O-- ~Id H(~ CH2CH2--C--O--.
~d (H3C)3C H3C
In the group of the fonnula lIa when r is 0, f is preferably 1 or 2.
2~8~6 Those composidons are preferred, wherein component (1) is a compound of the formula I, II, m, IV, V or VI, in particular I, II, m or IV.
Preferred compositions are those, wherein the hindered phenolic antioxidant corresponds to formula I and X is oxygen, b is an integer from 0 to 2, R2 and R3 are alkyl of 1 to B carbon atoms, A is oxygen, y is 2, R4 is hydrogen or a group of the formula la. Particularly preferred are those compounds wherein R2 and R3 are tert-butyl posidoned ortho to the hydroxyl group and b is 2. Compounds of preference are octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate and 2-ethylhexyl 3-(3',5',-di-tert butyl-~hydroxyphenyl)propionate.
Further prefeIred compositions are those, wherein the phenolic antioxidant corresponds to formula II and R2 and R3 are Cl-C8aL~cyl, in particular tert-butyl posidoned ortho to the hydroxyl group, b is 2, d is 2 or 4 and Q1 is C2-ClOaLtcylene or pentaerythritol. Specific compounds of preference are l,~hexamethylene bis[3',5'-di-tert-butyl-4'-hydroxyhydrocinnamate] and tetralds[methylene 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane.
Other preferred composidons contain compounds of formula II are those, wherein the hindered phenolic andoxidant corresponds to fo~mula lI, r is 0 and Q1 is formula IIa. A preferred compound of formula II when Ql is forrnula IIa is tris(3,5-di-tert.butyl-4-hydroxybenzyl)isocyanurate.
Preferred composidons are those, wherein dle hindered phenolic andoxidant corresponds to formula I~ and R2 and R3 are Cl-C8alkyl and preferably tert-butyl posidoned ortho to the hydroxyl group, b is 2 and Q2 is C2-C6alkylene. The specific compound of preference is N,N'-hexamethylene bis[3,5-di-tert-butyl-4-hydroxyhydrocinna nide].
Further, composidons containing compounds of for nula IV, wherein X and Y are oxygen, b is an integer from 0 to 2, R2 and R3 are allcyl of 1 to 8 carbon atoms, z is 2, e is an integer from 3 to 20, and R5 is a group of the formula Ia are preferred. Pardcularly prefeIred are those compounds, whereinR2 and R3 are tert-butyl posidoned ortho to the hydroxyl group. A
specific compound of preference is triethylene glycol bis[3-(3'-tert-butyl-S'-methyl4'-hydroxyphenyl)-propionate].
In preferred compositions containing compounds of formula VI R6 and R7 are methyl or 2~811~
tert-butyl and R8 and R9 are hydrogen or methyl. Specific compounds of preference are bis[2-hydroxy-3-tert-butyl-S-methylphenyl]methane and 1, 1-bis[2'-hydroxy-3',5 '~i-tert-butylphenyl]ethane.
A preferred compound of formula VII is OH OH
~C(CH3)3 (H3C)3C~¢I
¢I\C(CH3)3 (H3C)3C~
OH OH
A preferred composition contains a compound of formula vm, wherein Rlo is Cl-C4alkyl and most preferably methyl, Rll is C8-Cl2alkyl and most preferably n-octyl, and R13 is hydrogen.
Exarnples for hindered phenolic antioxidants are tetrakis[methylene-3-(3'-S'-di-tert.butyl-4'-hydroxyphenyl)propionate]methane, thiodiethylene bis(3,5-di-tert.butyl-4-hydroxy)hydrocinnamate, octadecyl 3-(3',5'-di-tert.butyl-4'-hydroxyphenyl)propionate, triethylene glycol bis-[3-(3'-tert.butyl-5'-methyl-4'-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,~tris-(3',5'-di-tert.butyl4'-hydroxybenzyl)benzene, 2,~di-tert butyl-p-cresol, tris(3,5-di-tert.butyl-4-hydroxybenzyl)isocyanurate, I,~hexamethylene bis(3,5~i-tert butyl-4-hydroxy-hydrociMamate, and 2,4-bis(n-octylthiomethyl)-~methylphenol.
Applicable phosphites correspond to the formulae 2~6~
~5~o~r ~
wherein Rl4 is tert.butyl, l,l-dimethylpropyl, cyclohexyl or phenyl, and one of Rls and Rl6 is hydrogen and the other is hydrogen, methyl, tert.butyl, 1,1-dimethylpropyl, cyclohexyl or phenyl;
[C9H19~ 3--P (X) *meaning isomer mixture of nonyl;
f--H2C~ ~CH2--0~
R170--P C P--OR17 (XI) \0--H2C CH2--0 Rl8 wherein Rl7 is n-Cl8H37, ~}Rlg or phenyl, Rl8, Rlg and R20 independently are Cl-CI8alkyl, R20 is also hydrogen and Rl9 is also D-COOR2l wherein D is a direct bond, methylene oq ethylene and R2l is Cl-Cl8alkyl and 206811~
C(CH3)3 o~ C(CU3h C(CH3)3 2 Preferred compositions contain compounds of formulae IX, X and XI.
A preferred compound of formula lX is tris(2,~di-tert.butylphenyl)phosphite. A preferred compound of formula XI is bis(2,4-di-teTt.butylphenyl)pentaary~ritol diphosphite.
Applicable phosphite co-stabiliærs include tris(2,4-di-tert.butylphenyl)phosphite, bis(2,4-di-tert.butylphenyl)pentaerythritol diphosphite, and tris~4-nonylphenyl)phosphite.
Applicable acid scavengers include epoxidiæd oils and alkali metal and aL~aline ear~ metal salts of higher fatty acids. The epoxidiæd oil is readily miscible in the adhesive fo~mulation.
Typical oils include epoxidized soy bean oil, epoxidized castor oil, epoxidiæd linseed oil and epoxidized sunflower oil, preferably epoxidized soy bean oil. Typical salts include calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate, preferably calcium stearate. Amines a~e also applicable including aLkanolamines such as triethanolamine and sterically hindered amines such as bis-(2,2,6,6-tetramethylpiperidyl)-sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5 di-tert.butyl-4-hydroxybenzyl malonic acid, bis-(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of l-hydroxyethyl-2,2,6,6-tetra~nethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert.octylamin~
2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,~tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl4-piperidyl)-1,2,3,4-butane-tetrac ar~onic acid and1,1,'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).
In preferred compositions the acid scavenger is epoxidized soy bean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized sunflower oil or calcium stearate.
206811~
The concentrations (by weight) of the respecdve components in the stabilizer system are as follows: from 25 to 74% of hindered phenol (c 1): and preferably 47.5%; from 5 to 74% of phosphite co-stabilizer (c 2), and preferably 25 to 74% and most preferably 47.5%; and from 2 to 50% of acid scavenger (c 3), preferably 2 to 10% and most preferably 5%.
The total amount of stabilizer system (c) added to the adhesive component is from 0.1-2.5%, preferably preferably 0.5-1.0% by weight based on the total adhesive formuladon.
Additional stabilizers may be opdonally incorpo¢ated into the adhesive compositions. Such additives include other antioxidants, light stabilizers and the like. Compositions containing (e) (mixed alkylated) diphenylamine antioxidants are particularly preferred. Typical alkyl groups include C4-CI8 alkyls.
The adhesive compositions of the present invention a~e typically prepared by blending the components at an elevated temperature, for example between 100C and 250C, preferably between 130C and 200C, until a homogeneous blend is obtained, usually less than 3 hours.
Various methods of blending are known to the art and any method that produces a homogeneous blend is satisfacto~y. The resultant adhesives may then preferably be used in a wide variety of product assembly applications.
The invention also pertains to a method for stabilizing a hot melt adhesive composition comprising an ethylene-vinyl acetate copolyrner and an effective tackifying amount of a hydrocarbon tackifying resin against oxidadve and thermal degradation which comprises incorporating into said hot melt adhesive composition (1) a phenolic antioxidant, (2) a phosphite co-stabilizer and (3) an acid scavenger se}ected from the group consisting of epoxidized oils, alkali metal salts of higher fatty acids and allcaline earth metal salts of higher fatty acids and amines.
The following examples illustrate the preferred embodiments of the invention. In these examples, all parts and percentages given are by weight unless other vise noted.
The following materials are employed in these examples:
"Adhesive" - 1:1:1 weight ratio of ethylene-vinyl acetate copolymer ((~LVAX 250 from DuPont): hydrogenated hydrocarbon tacldfier (~ARKON P-90 from Arakawa Chemical):microcrystalline wax (Bareco BE Square 195 from Petrolite).
2~S~1~ 6 A. tetrakis[methylene 3-(3',5'-di-tert butyl-4'-hydroxyphenyl)propionate]methaneB. thiodiethylene bis(3,5-di-tert.butyl-4-hydroxy)hydrocinnamate C. octadecyl3-(3',5'-di-tert.butyl-4'-hydroxyphenyl)propionate D. triethylene glycol bis[3-(3'-tert.butyl-S'-methyl-4'-hydroxyphenyl)propionate]
E. 1,3,5-trimethyl-2,4,~tris(3',5'-di-tert.butyl-4'-hydroxybenzyl)benæne F. 2,6-di-tert.butyl-p-cresol G. tris(3,5~i-tert.butyl-4-hydroxybenzyl)isocyanurate H. 1,6-hexamethylene bis(3,5-di-tert butyl~hydroxy-hydrocinnamate I. 2,4-bis(n-octylthiomethyl)-6~methylphenol J. tris(2,4-di-tert.butylphenyl)phosphite K. bis~2,4-di-tert butylphenyl)pentaerythritol diphosphite L. tris(4-nonylphenyl)phosphite M. epoxidized soy bean oil (Drapex 6.8 from Witco Chemical) N. epoxidized soy bean oil (Flexol from Union Carbide) P. (aL~cylatedmixture)diphenylamine Q. calcium stearate Example l This Example illustrates the improved performance characteristics provided by the compositions of this invention.
The a&esive composition ("A&esive") and additives are blended until homogeneous.Samples are then maintained in an oven at 177C and measured for color at periodic intenals utilizing a Gardner Color Scale.
The results are given below.
g = gray coloration b = black coloration Additive Conc. % Gardner Color I. 024 48 72 96 A 0.5 12 3 5 6 A 1.0 12 3 4 6 A/J 0.5/0.5 13 g A/J/M 0.5/0.510.05 1 1 2 3 4 A/J/N 0.5/0.5/0.05 1 2 2 3 4 II.
A/J 0.5/0.5 13 g A/J/M .49/.49/.021 2 3 4 5 A/J/~ .485/.485/.03 1 2 3 3 4 A/J/~ .48/.48/.041 2 3 3 4 A/J/M .475/.475/.05 1 2 3 3 4 m.*
A 1.0 0 2 5 6 7 A/J 0.5/0.5 0 3 g A/J/~ .475/.475/.05 0 1 2 2 3 A/J/M .49/.49/.0~ 0 0 1 2 3 * contains hydrogenated hydrocarbon tackfier (tg)ESCOREZ 5300 from Exxon) 2 ~
IV.
120 hrs A 0.5 0 33 4 4 6 A 1.0 0 33 4 4 6 J 0.5 0 2 g g g g A/M .5/.025 0 33 4 4 6 A/Q .5/.025 0 34 7 7 8 A/J .5/.5 0 48 b b b J/M .5/.025 0 26 10 11 12 J/Q .5/.025 0 36 9 11 12 A/J/M .5/.5/.05 0 11 2 3 5 A/J/Q .5/.5/.05 0 11 3 4 5 Example 3 The procedures of Example 1 are repeated wi~ a series of addi~onal hindered phenols.
Additive Conc. (%) Gardner Color J 1.0 0 g b A 1.0 0 3 5 5 5 A/J O.S/0.5 0 4 b A/J/M .nsl.ns/.os o 3 3 4 6 B 1.0 0 4S 10 11 B/J 0.5/0.5 0 gb B~ .475/.475/.05 03 3 4 6 C 1.0 0 45 5 6 Cl~ 0.5/0.5 0 5b C/J/M .475/.475/.05 o3 4 4 4 20681~ ~
D 1.0 0 5 6 7 7 D/~ 0.5/0.5 0 g b - -D/J/M .475/.475/.05 0 3 5 6 6 E 1.0 0 6 6 7 7 E/J 0.5/0.5 0 g b E/J/~I .475/.475/.05 0 3 4 5 6 F 1.0 0 6 910 10 F/J 0.5/0.5 0 4 b ~/J/M .475/.475/.05 0 3 3 4 6 G 1.0 0 5 6 7 7 G/J 0.5/0.5 0 g b G/J/M .475/.475/.05 0 3 3 3 4 H 1.0 0 4 6 6 7 HlJ 0.5/0.5 0 g b - -H/J/M .475/.475/.05 0 2 3 3 4 1.0 0 4 610 12 VJ 0.5/0.5 0 g b - -VJ~M .475/.475/.05 0 3 611 11 P/A 0.5/0.5 0 4 5 6 7 P/A/J .25/.25/.5 0 5 b - -P/A/J/M 24/.24/.47/.05 0 1 2 3 4 The data in Examples 1 and 2 clearly illustrate the significandy improved stabilization characteristics provided to the ethylene-vinyl acetate hot melt adhesive formulations.
Summarizing, it is seen that this invention provi~es improved stabilization systems ~or use in ethylene-vinyl acetate hot melt adhesive compositions containing hydrogenated hydrocarbon tackifying resins. Vatiations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
The primary components of the hot melt adhesive system are ethylene-vinyl acetate copolymer, a hydrocarbon tackifying resin and, opdonally, petroleum derived waxes and various plasticizing oils.
The applicable tackifying resins may be described as hydrogenated and non-hydrogenated aliphatic petroleum hydrocarbon resins (preferably hydrogenated varieties) resulting from the polymerization of monomers consisting primarily of mono- and diolefins, hydrogenated and non-hydrogenated aromatic petroleum hydrocarbon resins and hydrogenated and non-hydrogenated alicyclic petroleum hydrocarbon resins. Additionally, hydrogenated and non-hydrogenated polyteIpene hydrocarbon resins may be used as the tackifying resin.
Mixtures of the above are also applicable. Such tackifying resins for example are present in concentrations ranging from 10 to 90%, by weight, and preferably 2S to 50%, by weight. The particular resin is selected on the basis of compatibility with the adhesive system, with 20~811~
colorless or white tacldfiers being paTticularly preferred. (~)ARKON P-90 from Arakawa Chemical, (~)ESCOREZ 5300 from Exxon Chemical and ~\REGALREZ 1094 from Hercules,for example, are typical commercial tacldfying resins.
Preferred composidons are those, wherein said hydrocarbon tackifying resin is selected from the group consisting of aliphatic petroleum hydrocarbon resins and hydrogenated derivatives thereof, aromadc petroleum hydrocarbon resins and hydrogenated deIivatives thereof and alicyclic petroleum hydrocarbon resins and hydrogenated derivatives thereof, polyterpene hydrocarbon resins and hydrogenated derivatdves thereof, and mixtures thereof. Pardcularly preferred are those, wherein said hydrocarbon tackifying resin is hydrogenated.
The petroleum derived waxes are optionally present in concentrations ranging from 0 to 50%, by weight, and serve to impart greater fluidity to the molten mateAal, flexibility to the set adhesive and wefflng characteristics. Paraffin and microcrystalline waxes with melting points of 55-110C as well as polyethylene or Fischer-Tropsch waxes are illustrative of this component.
The composition described above may additionally contain (d) up to 50% by weight of a petroleum derived wax, based on components (a) and (b). In these compositions components (a), (b) and (d) are preferably present in a weight ratio of 1:1:1.
These plasticizing or extending oils are also present in order to provide wetting action and viscosity control. Concentrations from 1 to 50%, by weight, are applicable. Typical oils include ole~m oligomers, vegetable and animal oils and naphthenic oils.
In the compositions of the present invention components (a) and (b) are present in a weight ratio of 10:90 to 90:10, especially 25:75 to 75:25.
The combination of stabilizers which substantially eliminates heat degradation, color formation, undesirable viscosity changes and sldn formation comprise (1~ a hindered phenolic antioxidant;
(2) a phosphite co-stabilizer; and (3) an acid scavenger.
206811 ~
Hindered phenols are well known to those skilled in the art.
The composition of the present invention comprises hindered phenolic antioxidants corresponding to the formulae RlX~(CIlH2a)~Q (1) wherein Rl is a group of the formula Ia, H~}(CbH2b)-- I-- (Ia) X is oxygen or sulfur, a is an integer from 6 to 30, preferably 6 to 18, b is an integer from 0 to 6, R2 and R3 are independently Cl-Cl8aL~cyl, Cs-Cl2cycloaL~yl, phenyl or CrC9aralkyl, and R2 is also hydrogen, Q is hydrogen or -A-(C~H2y)~R4~ A is oxygen, sulfur or--Nl--, y iS an integer from 2 to 20, I3 is Cl-C4aL~cyl or Cl-C4alkanoyl, and R4 is hydrogen, hydroxy, Cl-C4alkanoyloxy or a group of the formula Ib, H~(CbH2b)--C---- (Ib);
u~(CbH2b)--C--o~Ql wherein R2, R3 and b are as defined above, r is 1, d is an integer from 2 to 6, and Ql is a divalent aliphatic hydrocarbon of 1 to 18 carbon atoms, a divalent aromatic or aromatic aliphatic hydrocarbon of 6 to 20 carbon atoms or a group of the formula Ila when r is also 0 206~116 (H2C)f N N--(CH2)~
O~N~o (IIa) (Cl H2~f wherein f is an integer from 1 to 4;
L ~ (CbH2b)--C--1 ~ Q2 wherein R2, R3 and b are as defined above, and Q2 iS Cl-C18alkylene;
RlX-[(CzH2~)~Ye~R5 aV) wherein Rl and X are as defined above, z is an integer ~om 2 to 6, e is an integer from 3 to 40, preferably 3 to 10, Y is oxygen or sul~r, and Rs is hydrogen, Cl-C4aLlcyl or a group of the formula Ia;
2 ~
(H3C)3C C(CH3)3 HO~CHH~OH
CH3 ¦ H3C
CHCH3 (V);
H3C~p~
~\C(CH3)3 OH
OH OH
R6~ ~R6 R~ Al~R7 (VI) wherein R6 and R7 are independendy Cl-Cl8alkyl, Cs-C~2cycloaL~cyl, phenyl or C7-C9araL~cyl, and R6 is also hydrogen, and Al is a group ~C(Rg)Rg wherein R8 and Rg are independently hydrogen or Cl-C6aLIcyl;
OH
R3~ l H3C--C--(CpH2p)--C--O- -3 (VII) OH
wherein R3 iS as defined above, p is 1 or 2 and Q3 iS C2-CIOalkylene; and OH
Rl~CHz--S--Rll CH2~ S--Rl 1 wherein Rlo is Cl-ClOallyl or Cs-CI2cycloaL~cyl, Rll independently is Cl-C18alkyl, phenyl or benzyl and R12 iS hydrogen or methyl.
ALkyl is straight chain or branched as for example methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, decyl, undecyl, dodecyl or octadecyl.
Cl-CI8alkyloxy is for example methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy or octadecyloxy.
Cl-C4alkanoyl is for example acetyl, propionyl or butyryl.
Cl-C4aL~canoyloxy is for example acetyloxy, propionyloxy or butyryloxy.
C5-Cl2cycloaL~cyl is for example cyclopentyl, cyclohexyl or cyclooctyl. Cyclohexyl is preferred.
CTCgarallyl is in particular C7-CgphenylaL~cyl~ for example benzyl, a-methylbenzyl, a,a-dimethylbenzyl orphenylethyl. Benzyl is preferred.
Cl-CI8alkylene is for exa nple methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene.
For compounds of forrnula II when r is 1, Ql as a divalent hydrocarbon is e.g. straight-chain or branched C2-Cl8aL~tylene, preferably C2-CIOallcylene, or C2-C6aL~ylidene such as, for example, ethylene, ethylidene, tIimethylene, tetramethylene, pentamethylene, 2,2~imethylpropane-1,3-diyl, hexamethylene, heptamethylene, octarnethylene, 206~
decamethylene, 2,2-pentamethylene-propane-1,3-diyl, and cyclohexylene or Ql as a divalent aromatic or aliphatic aromatic hydrocarbon of 6 to 20 carbon atoms is e.g. unsubstituted or substituted C6-ClOarylene such as, for example, phenylene, phenylene substituted by one or more, for example 1 to 3 Cl-C4aL~cyl, naphthylene or ~ C~
Ql as a trivalent, tetravalent or pentavalent hydrocarbon is, for exarnple, a group of the following formulae b ~ ~ ~,~
alkanetriyl of 3 to 6 carbon atoms, such as e.g. glyceryl or trimethylylpropane or alkanetetrayl of 4 to 6 carbon atoms such as e.g. pentaerythrityl.
Formula Ia represents preferably one of the following groups:
(H3C)3C (H3C)3C
H~ CH2CH2--C-- ~ H~ CH2CHz--C--(H3c)3c H3C
Formula Ib is in particular one of the groups (H3C)3C (H3C)3C
H~ CH2CHz--~C--O-- ~Id H(~ CH2CH2--C--O--.
~d (H3C)3C H3C
In the group of the fonnula lIa when r is 0, f is preferably 1 or 2.
2~8~6 Those composidons are preferred, wherein component (1) is a compound of the formula I, II, m, IV, V or VI, in particular I, II, m or IV.
Preferred compositions are those, wherein the hindered phenolic antioxidant corresponds to formula I and X is oxygen, b is an integer from 0 to 2, R2 and R3 are alkyl of 1 to B carbon atoms, A is oxygen, y is 2, R4 is hydrogen or a group of the formula la. Particularly preferred are those compounds wherein R2 and R3 are tert-butyl posidoned ortho to the hydroxyl group and b is 2. Compounds of preference are octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate and 2-ethylhexyl 3-(3',5',-di-tert butyl-~hydroxyphenyl)propionate.
Further prefeIred compositions are those, wherein the phenolic antioxidant corresponds to formula II and R2 and R3 are Cl-C8aL~cyl, in particular tert-butyl posidoned ortho to the hydroxyl group, b is 2, d is 2 or 4 and Q1 is C2-ClOaLtcylene or pentaerythritol. Specific compounds of preference are l,~hexamethylene bis[3',5'-di-tert-butyl-4'-hydroxyhydrocinnamate] and tetralds[methylene 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane.
Other preferred composidons contain compounds of formula II are those, wherein the hindered phenolic andoxidant corresponds to fo~mula lI, r is 0 and Q1 is formula IIa. A preferred compound of formula II when Ql is forrnula IIa is tris(3,5-di-tert.butyl-4-hydroxybenzyl)isocyanurate.
Preferred composidons are those, wherein dle hindered phenolic andoxidant corresponds to formula I~ and R2 and R3 are Cl-C8alkyl and preferably tert-butyl posidoned ortho to the hydroxyl group, b is 2 and Q2 is C2-C6alkylene. The specific compound of preference is N,N'-hexamethylene bis[3,5-di-tert-butyl-4-hydroxyhydrocinna nide].
Further, composidons containing compounds of for nula IV, wherein X and Y are oxygen, b is an integer from 0 to 2, R2 and R3 are allcyl of 1 to 8 carbon atoms, z is 2, e is an integer from 3 to 20, and R5 is a group of the formula Ia are preferred. Pardcularly prefeIred are those compounds, whereinR2 and R3 are tert-butyl posidoned ortho to the hydroxyl group. A
specific compound of preference is triethylene glycol bis[3-(3'-tert-butyl-S'-methyl4'-hydroxyphenyl)-propionate].
In preferred compositions containing compounds of formula VI R6 and R7 are methyl or 2~811~
tert-butyl and R8 and R9 are hydrogen or methyl. Specific compounds of preference are bis[2-hydroxy-3-tert-butyl-S-methylphenyl]methane and 1, 1-bis[2'-hydroxy-3',5 '~i-tert-butylphenyl]ethane.
A preferred compound of formula VII is OH OH
~C(CH3)3 (H3C)3C~¢I
¢I\C(CH3)3 (H3C)3C~
OH OH
A preferred composition contains a compound of formula vm, wherein Rlo is Cl-C4alkyl and most preferably methyl, Rll is C8-Cl2alkyl and most preferably n-octyl, and R13 is hydrogen.
Exarnples for hindered phenolic antioxidants are tetrakis[methylene-3-(3'-S'-di-tert.butyl-4'-hydroxyphenyl)propionate]methane, thiodiethylene bis(3,5-di-tert.butyl-4-hydroxy)hydrocinnamate, octadecyl 3-(3',5'-di-tert.butyl-4'-hydroxyphenyl)propionate, triethylene glycol bis-[3-(3'-tert.butyl-5'-methyl-4'-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,~tris-(3',5'-di-tert.butyl4'-hydroxybenzyl)benzene, 2,~di-tert butyl-p-cresol, tris(3,5-di-tert.butyl-4-hydroxybenzyl)isocyanurate, I,~hexamethylene bis(3,5~i-tert butyl-4-hydroxy-hydrociMamate, and 2,4-bis(n-octylthiomethyl)-~methylphenol.
Applicable phosphites correspond to the formulae 2~6~
~5~o~r ~
wherein Rl4 is tert.butyl, l,l-dimethylpropyl, cyclohexyl or phenyl, and one of Rls and Rl6 is hydrogen and the other is hydrogen, methyl, tert.butyl, 1,1-dimethylpropyl, cyclohexyl or phenyl;
[C9H19~ 3--P (X) *meaning isomer mixture of nonyl;
f--H2C~ ~CH2--0~
R170--P C P--OR17 (XI) \0--H2C CH2--0 Rl8 wherein Rl7 is n-Cl8H37, ~}Rlg or phenyl, Rl8, Rlg and R20 independently are Cl-CI8alkyl, R20 is also hydrogen and Rl9 is also D-COOR2l wherein D is a direct bond, methylene oq ethylene and R2l is Cl-Cl8alkyl and 206811~
C(CH3)3 o~ C(CU3h C(CH3)3 2 Preferred compositions contain compounds of formulae IX, X and XI.
A preferred compound of formula lX is tris(2,~di-tert.butylphenyl)phosphite. A preferred compound of formula XI is bis(2,4-di-teTt.butylphenyl)pentaary~ritol diphosphite.
Applicable phosphite co-stabiliærs include tris(2,4-di-tert.butylphenyl)phosphite, bis(2,4-di-tert.butylphenyl)pentaerythritol diphosphite, and tris~4-nonylphenyl)phosphite.
Applicable acid scavengers include epoxidiæd oils and alkali metal and aL~aline ear~ metal salts of higher fatty acids. The epoxidiæd oil is readily miscible in the adhesive fo~mulation.
Typical oils include epoxidized soy bean oil, epoxidized castor oil, epoxidiæd linseed oil and epoxidized sunflower oil, preferably epoxidized soy bean oil. Typical salts include calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate, preferably calcium stearate. Amines a~e also applicable including aLkanolamines such as triethanolamine and sterically hindered amines such as bis-(2,2,6,6-tetramethylpiperidyl)-sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5 di-tert.butyl-4-hydroxybenzyl malonic acid, bis-(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of l-hydroxyethyl-2,2,6,6-tetra~nethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert.octylamin~
2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,~tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl4-piperidyl)-1,2,3,4-butane-tetrac ar~onic acid and1,1,'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).
In preferred compositions the acid scavenger is epoxidized soy bean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized sunflower oil or calcium stearate.
206811~
The concentrations (by weight) of the respecdve components in the stabilizer system are as follows: from 25 to 74% of hindered phenol (c 1): and preferably 47.5%; from 5 to 74% of phosphite co-stabilizer (c 2), and preferably 25 to 74% and most preferably 47.5%; and from 2 to 50% of acid scavenger (c 3), preferably 2 to 10% and most preferably 5%.
The total amount of stabilizer system (c) added to the adhesive component is from 0.1-2.5%, preferably preferably 0.5-1.0% by weight based on the total adhesive formuladon.
Additional stabilizers may be opdonally incorpo¢ated into the adhesive compositions. Such additives include other antioxidants, light stabilizers and the like. Compositions containing (e) (mixed alkylated) diphenylamine antioxidants are particularly preferred. Typical alkyl groups include C4-CI8 alkyls.
The adhesive compositions of the present invention a~e typically prepared by blending the components at an elevated temperature, for example between 100C and 250C, preferably between 130C and 200C, until a homogeneous blend is obtained, usually less than 3 hours.
Various methods of blending are known to the art and any method that produces a homogeneous blend is satisfacto~y. The resultant adhesives may then preferably be used in a wide variety of product assembly applications.
The invention also pertains to a method for stabilizing a hot melt adhesive composition comprising an ethylene-vinyl acetate copolyrner and an effective tackifying amount of a hydrocarbon tackifying resin against oxidadve and thermal degradation which comprises incorporating into said hot melt adhesive composition (1) a phenolic antioxidant, (2) a phosphite co-stabilizer and (3) an acid scavenger se}ected from the group consisting of epoxidized oils, alkali metal salts of higher fatty acids and allcaline earth metal salts of higher fatty acids and amines.
The following examples illustrate the preferred embodiments of the invention. In these examples, all parts and percentages given are by weight unless other vise noted.
The following materials are employed in these examples:
"Adhesive" - 1:1:1 weight ratio of ethylene-vinyl acetate copolymer ((~LVAX 250 from DuPont): hydrogenated hydrocarbon tacldfier (~ARKON P-90 from Arakawa Chemical):microcrystalline wax (Bareco BE Square 195 from Petrolite).
2~S~1~ 6 A. tetrakis[methylene 3-(3',5'-di-tert butyl-4'-hydroxyphenyl)propionate]methaneB. thiodiethylene bis(3,5-di-tert.butyl-4-hydroxy)hydrocinnamate C. octadecyl3-(3',5'-di-tert.butyl-4'-hydroxyphenyl)propionate D. triethylene glycol bis[3-(3'-tert.butyl-S'-methyl-4'-hydroxyphenyl)propionate]
E. 1,3,5-trimethyl-2,4,~tris(3',5'-di-tert.butyl-4'-hydroxybenzyl)benæne F. 2,6-di-tert.butyl-p-cresol G. tris(3,5~i-tert.butyl-4-hydroxybenzyl)isocyanurate H. 1,6-hexamethylene bis(3,5-di-tert butyl~hydroxy-hydrocinnamate I. 2,4-bis(n-octylthiomethyl)-6~methylphenol J. tris(2,4-di-tert.butylphenyl)phosphite K. bis~2,4-di-tert butylphenyl)pentaerythritol diphosphite L. tris(4-nonylphenyl)phosphite M. epoxidized soy bean oil (Drapex 6.8 from Witco Chemical) N. epoxidized soy bean oil (Flexol from Union Carbide) P. (aL~cylatedmixture)diphenylamine Q. calcium stearate Example l This Example illustrates the improved performance characteristics provided by the compositions of this invention.
The a&esive composition ("A&esive") and additives are blended until homogeneous.Samples are then maintained in an oven at 177C and measured for color at periodic intenals utilizing a Gardner Color Scale.
The results are given below.
g = gray coloration b = black coloration Additive Conc. % Gardner Color I. 024 48 72 96 A 0.5 12 3 5 6 A 1.0 12 3 4 6 A/J 0.5/0.5 13 g A/J/M 0.5/0.510.05 1 1 2 3 4 A/J/N 0.5/0.5/0.05 1 2 2 3 4 II.
A/J 0.5/0.5 13 g A/J/M .49/.49/.021 2 3 4 5 A/J/~ .485/.485/.03 1 2 3 3 4 A/J/~ .48/.48/.041 2 3 3 4 A/J/M .475/.475/.05 1 2 3 3 4 m.*
A 1.0 0 2 5 6 7 A/J 0.5/0.5 0 3 g A/J/~ .475/.475/.05 0 1 2 2 3 A/J/M .49/.49/.0~ 0 0 1 2 3 * contains hydrogenated hydrocarbon tackfier (tg)ESCOREZ 5300 from Exxon) 2 ~
IV.
120 hrs A 0.5 0 33 4 4 6 A 1.0 0 33 4 4 6 J 0.5 0 2 g g g g A/M .5/.025 0 33 4 4 6 A/Q .5/.025 0 34 7 7 8 A/J .5/.5 0 48 b b b J/M .5/.025 0 26 10 11 12 J/Q .5/.025 0 36 9 11 12 A/J/M .5/.5/.05 0 11 2 3 5 A/J/Q .5/.5/.05 0 11 3 4 5 Example 3 The procedures of Example 1 are repeated wi~ a series of addi~onal hindered phenols.
Additive Conc. (%) Gardner Color J 1.0 0 g b A 1.0 0 3 5 5 5 A/J O.S/0.5 0 4 b A/J/M .nsl.ns/.os o 3 3 4 6 B 1.0 0 4S 10 11 B/J 0.5/0.5 0 gb B~ .475/.475/.05 03 3 4 6 C 1.0 0 45 5 6 Cl~ 0.5/0.5 0 5b C/J/M .475/.475/.05 o3 4 4 4 20681~ ~
D 1.0 0 5 6 7 7 D/~ 0.5/0.5 0 g b - -D/J/M .475/.475/.05 0 3 5 6 6 E 1.0 0 6 6 7 7 E/J 0.5/0.5 0 g b E/J/~I .475/.475/.05 0 3 4 5 6 F 1.0 0 6 910 10 F/J 0.5/0.5 0 4 b ~/J/M .475/.475/.05 0 3 3 4 6 G 1.0 0 5 6 7 7 G/J 0.5/0.5 0 g b G/J/M .475/.475/.05 0 3 3 3 4 H 1.0 0 4 6 6 7 HlJ 0.5/0.5 0 g b - -H/J/M .475/.475/.05 0 2 3 3 4 1.0 0 4 610 12 VJ 0.5/0.5 0 g b - -VJ~M .475/.475/.05 0 3 611 11 P/A 0.5/0.5 0 4 5 6 7 P/A/J .25/.25/.5 0 5 b - -P/A/J/M 24/.24/.47/.05 0 1 2 3 4 The data in Examples 1 and 2 clearly illustrate the significandy improved stabilization characteristics provided to the ethylene-vinyl acetate hot melt adhesive formulations.
Summarizing, it is seen that this invention provi~es improved stabilization systems ~or use in ethylene-vinyl acetate hot melt adhesive compositions containing hydrogenated hydrocarbon tackifying resins. Vatiations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
Claims (14)
1. A stabilized hot melt adhesive composition comprising (a) ethylene-vinyl acetate copolymer, (b) a hydrocarbon tackifying resin; and (c) a stabilizer composition comprising (1) a phenolic antioxidant;
(2) a phosphite co-stabilizer; and (3) an acid scavenger selected from the group consisting of epoxidized oils, alkali metal salts of higher fatty acids, alkaline earth metal salts of higher fatty acids and amines.
(2) a phosphite co-stabilizer; and (3) an acid scavenger selected from the group consisting of epoxidized oils, alkali metal salts of higher fatty acids, alkaline earth metal salts of higher fatty acids and amines.
2. The composition of claim 1, wherein components (a) and (b) are present in a weight ratio of 10:90 to 90:10, especially 25:75 to 75:25.
3. The composition of claim 1, which additionally contains (d) up to 50% by weight of a petroleum derived wax, based on components (a) and (b).
4. The composition of claim 1, wherein said hindered phenolic antioxidant corresponds to the formula R1X-(CaH2a)-Q (I) wherein R1 is a group of the formula Ia, (Ia) X is oxygen or sulfur, a is an integer from 6 to 30, b is an integer from O to 6, R2 and R3 are independently C1-C18alkyl, C5-C12cycloalkyl, phenyl or C7-C9aralkyl, and R2 is also hydrogen, Q is hydrogen or -A-(CH2y)-R4, A is oxygen, sulfur or , y is an integer from 2 to 20, B is C1-C4alkyl or C1-C4alkanoyl, and R4 is hydrogen, hydroxy, C1-C4alkanoyloxy or a group of the formula Ib, (Ib);
(II) wherein R2, R3 and b are as defined above, r is 1, d is an integer from 2 to 6, and Q1 is a divalent aliphatic hydrocarbon of 1 to 18 carbon atoms, a divalent aromatic or aromatic aliphatic hydrocarbon of 6 to 20 carbon atoms or a group of the formula IIa when r is also 0 (IIa) wherein f is an integer from 1 to 4;
(III) wherein R2, R3 and b are as defined above, and Q2 is C1-C18alkylene;
R1X-[(CzH2z)-Y]e-R5 (IV) wherein R1 and X are as defined above, z is an integer from 2 to 6, e is an integer from 3 to 40, Y is oxygen or sulfur, and R5 is hydrogen, C1-C4alkyl or a group of the formula Ia;
(V);
wherein R6 and R7 are independently C1-C18alkyl, C5-C12cycloalkyl, phenyl or C7-C9aralkyl, and R6 is also hydrogen, and A1 is a group wherein R8 and R9 are independently hydrogen or C1-C6alkyl;
(VII) wherein R3 is as defined above, p is 1 or 2 and Q3 is C2-C10alkylene; or (VIII) wherein R10 is C1-C10alkyl or C5-C12cycloalkyl, R11 independently is C1-C18alkyl, phenyl or benzyl and R12 is hydrogen or methyl.
(II) wherein R2, R3 and b are as defined above, r is 1, d is an integer from 2 to 6, and Q1 is a divalent aliphatic hydrocarbon of 1 to 18 carbon atoms, a divalent aromatic or aromatic aliphatic hydrocarbon of 6 to 20 carbon atoms or a group of the formula IIa when r is also 0 (IIa) wherein f is an integer from 1 to 4;
(III) wherein R2, R3 and b are as defined above, and Q2 is C1-C18alkylene;
R1X-[(CzH2z)-Y]e-R5 (IV) wherein R1 and X are as defined above, z is an integer from 2 to 6, e is an integer from 3 to 40, Y is oxygen or sulfur, and R5 is hydrogen, C1-C4alkyl or a group of the formula Ia;
(V);
wherein R6 and R7 are independently C1-C18alkyl, C5-C12cycloalkyl, phenyl or C7-C9aralkyl, and R6 is also hydrogen, and A1 is a group wherein R8 and R9 are independently hydrogen or C1-C6alkyl;
(VII) wherein R3 is as defined above, p is 1 or 2 and Q3 is C2-C10alkylene; or (VIII) wherein R10 is C1-C10alkyl or C5-C12cycloalkyl, R11 independently is C1-C18alkyl, phenyl or benzyl and R12 is hydrogen or methyl.
5. The composition of claim 4, wherein the hindered phenolic antioxidant corresponds to formula I and X is oxygen, b is an integer from 0 to 2, R2 and R3 are alkyl of 1 to 8 carbon atoms, A is oxygen, y is 2 and R4 is hydrogen or a group of the formula Ia.
6. The composition of claim 4, wherein the hindered phenolic antioxidant corresponds to formula II and r is 1, R2 and R3 are C1-C8alkyl, b is 2, d is 2 or 4 and Q1 is C2-C10alkylene or pentaerythritol.
7. The composition of claim 4, wherein the hindered phenolic antioxidant corresponds to formula m and R2 and R3 are C1-C8 alkyl, b is 2 and Q2 is C2-C6 alkylene.
8. The composition of claim 4, wherein the hindered phenolic antioxidant corresponds to formula IV and X and Y are oxygen, b is 0-2, R2 and R3 are C1-C8 alkyl, z is 2, e is 3-20 and R5 is a group of formula Ia.
9. The composition of claim 1, wherein said phosphite co-stabilizer corresponds to the formulae (IX) wherein R14 is tert.butyl, 1,1-dimethylpropyl, cyclohexyl or phenyl, and one of R15 and R16 is hydrogen and the other is hydrogen, methyl, tert.butyl, 1,1-dimethylpropyl, cyclohexyl or phenyl;
(X) *indicates an isomeric mixture of nonyl;
(XI) wherein R17 is n-C18H37, or phenyl, R18, R19 and R20 independently are C1-C8alkyl, R20 is also hydrogen andR19 is also D-COOR21 wherein D is a direct bond, methylene or ethylene and R21 is C1-C18alkyl; or (XII).
(X) *indicates an isomeric mixture of nonyl;
(XI) wherein R17 is n-C18H37, or phenyl, R18, R19 and R20 independently are C1-C8alkyl, R20 is also hydrogen andR19 is also D-COOR21 wherein D is a direct bond, methylene or ethylene and R21 is C1-C18alkyl; or (XII).
10. The composition of claim 9, wherein the phosphite corresponds to formula IX, X or XI.
11. The composition of claim 1, wherein said acid scavenger is epoxidized soy bean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized sunflower oil or calcium stearate.
12. The composition of claim 1, wherein component (c) is present in a concentration of 0.1-2.5%, preferably 0.5-1,0% by weight based on the total adhesive composition.
13. The composition of claim 1, which additionally contains (e) a (mixed alkylated) diphenylamine antioxidant.
14. A method for stabilizing a hot melt adhesive composition comprising an ethylene-vinyl acetate copolymer and an effective tackifying amount of a hydrocarbon tackifying resin against oxidative and thermal degradation which comprises incorporating into said hot melt adhesive composition (1) a phenolic andoxidant, (2) a phosphite co-stabilizer and (3) an acid scavenger selected from the group consisting of epoxidized oils, alkali metal salts of higher fatty acids and alkaline earth metal salts of higher fatty acids and amines.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US697,837 | 1991-05-09 | ||
| US07/697,837 US5128397A (en) | 1991-05-09 | 1991-05-09 | Stabilized ethylene-vinyl acetate copolymer hot melt adhesive systems |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2068116A1 true CA2068116A1 (en) | 1992-11-10 |
Family
ID=24802783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002068116A Abandoned CA2068116A1 (en) | 1991-05-09 | 1992-05-07 | Stabilized hot melt adhesive systems |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5128397A (en) |
| EP (1) | EP0512955B1 (en) |
| JP (1) | JPH05156221A (en) |
| CA (1) | CA2068116A1 (en) |
| DE (1) | DE69202919T2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW222293B (en) * | 1991-12-06 | 1994-04-11 | Ciba Geigy Ag | |
| JP3499587B2 (en) * | 1993-10-05 | 2004-02-23 | 旭電化工業株式会社 | Hot melt adhesive with improved heat resistance |
| US5541246A (en) * | 1994-10-24 | 1996-07-30 | Arizona Chemical Company | Repulpable hot melt adhesives |
| US7331533B2 (en) * | 1996-03-06 | 2008-02-19 | Compositech, L.L.C. | Thermoplastic railroad cross-ties |
| WO1999041065A1 (en) * | 1996-03-06 | 1999-08-19 | Compositech, Llc. | Thermoplastic articles made from recycled products and process for making |
| US6500877B1 (en) * | 1999-11-05 | 2002-12-31 | Krohn Industries, Inc. | UV curable paint compositions and method of making and applying same |
| US7323239B2 (en) * | 2001-10-22 | 2008-01-29 | Exxonmobil Chemical Patents Inc. | Protective films |
| AU2003282521A1 (en) * | 2002-10-09 | 2004-05-04 | Exxonmobil Chemical Patents Inc. | Heat sealable compositions and uses thereof |
| US6984680B2 (en) * | 2003-04-15 | 2006-01-10 | Adherent Laboratories, Inc. | Low odor, light color hot pick-up adhesive |
| WO2007097511A1 (en) * | 2006-02-24 | 2007-08-30 | Lg Chem, Ltd. | Cross-linked polyethylene having excellent inhibition of sweat-out and insulation properties |
| JP5563987B2 (en) * | 2008-11-04 | 2014-07-30 | 株式会社ブリヂストン | Adhesive sheet and solar cell using the same |
| KR101722762B1 (en) * | 2013-03-25 | 2017-04-05 | (주)에버텍엔터프라이즈 | Two-component type adhesive composition comprising eco-friendly resin made from biomass |
| KR101478747B1 (en) * | 2013-03-25 | 2015-01-05 | (주)에버텍엔터프라이즈 | Two-component type adhesive composition with improved tensile and hygroscopic properties |
| GB201318489D0 (en) * | 2013-10-18 | 2013-12-04 | Addivant Switzerland Gmbh | Composition |
| US11725122B2 (en) * | 2019-01-31 | 2023-08-15 | Synthomer Adhesive Technologies Llc | Processes for making low volatile tackifier compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3658743A (en) * | 1970-04-30 | 1972-04-25 | Uniroyal Inc | Stabilization of unsaturated hydrocarbon elastomers by synergistic combination of a phenolic compound an organic sulfide or thioester and an epoxide or phosphite ester |
| GB1414635A (en) * | 1971-11-19 | 1975-11-19 | Evode Ltd | Hot melt adhesives |
| CH626385A5 (en) * | 1976-02-05 | 1981-11-13 | Ciba Geigy Ag | |
| US4283317A (en) * | 1980-09-15 | 1981-08-11 | E. I. Du Pont De Nemours And Company | Wax-free, hot melt adhesive compositions |
| ES2014433B3 (en) * | 1985-11-13 | 1990-07-16 | Ciba-Geigy Ag | SUBSTITUTED PHENOLS, AS STABILIZERS. |
| US4835200A (en) * | 1986-12-19 | 1989-05-30 | Shell Oil Company | Color stable hot melt adhesive |
| DE3851586T2 (en) * | 1987-07-16 | 1995-05-24 | Asahi Chemical Ind | Composition of a specific block copolymer and process for its preparation. |
-
1991
- 1991-05-09 US US07/697,837 patent/US5128397A/en not_active Expired - Fee Related
-
1992
- 1992-04-29 EP EP92810317A patent/EP0512955B1/en not_active Expired - Lifetime
- 1992-04-29 DE DE69202919T patent/DE69202919T2/en not_active Expired - Fee Related
- 1992-05-07 JP JP4142237A patent/JPH05156221A/en active Pending
- 1992-05-07 CA CA002068116A patent/CA2068116A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US5128397A (en) | 1992-07-07 |
| DE69202919T2 (en) | 1995-11-16 |
| EP0512955B1 (en) | 1995-06-14 |
| EP0512955A1 (en) | 1992-11-11 |
| DE69202919D1 (en) | 1995-07-20 |
| JPH05156221A (en) | 1993-06-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |